Oxime carbamate phosphate, phosphonate, phosphinate and phosphoroamidates

ABSTRACT

Oxime carbamate phosphates, phosphonates, phosphinates and phosphoroamidates having the general formula: IN WHICH X and Y are independently selected from the group consisting of oxygen and sulfur; R is selected from the group lower alkyl or lower alkoxy, having from one to six carbon atoms inclusive; R1 is selected from the group consisting of lower alkyl or lower alkoxy having from one to six carbon atoms, inclusive, amino, lower alkyl-substituted amino and phenyl; Q is selected from the group consisting of divalent tetramethylenediene-1,3, lower alkoxy or lower alkyl having from one to four carbon atoms inclusive, each, nitro, halogen and combinations thereof, and lower dialkyl-substituted thionophosphoryloxy; R2 is selected from the the group consisting of hydrogen, lower alkyl having from one to four carbon atoms, and phenyl; and R3 is selected from the group consisting of hydrogen; substituted carbonate and thiocarbonates of the type IN WHICH Z is oxygen or sulfur, R4 is lower alkyl having from one to four carbon atoms, inclusive, and Beta -chloro-loweralkyl having from two to four carbon atoms; carbamates of the type IN WHICH R5 and R6 are independently selected from the group consisting of hydrogen, alkyl having from one to ten carbons, inclusive, substituted alkyl having one to six carbon atoms inclusive, said substituents selected from the group consisting of hydroxy, halogen, amino, di-lower-alkyl amino, lower alkoxy, and tetrahydrofuryl; lower alkenyl having from two to four carbons, inclusive, carboalkoxy alkyl having a total of from three to eight carbon atoms, inclusive, cycloalkyl having from three to six carbon atoms, inclusive, piperazino, 2-thiazolyl, phenyl, naphthyl, substituted phenyl wherein said substituents are selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower thioalkyl, lower dialkylamino in which said lower alkyl and lower alkoxy moieties have from one to four carbon atoms, inclusive, nitro, cyano, trifluoromethyl, and combinations thereof; and in which IS AN N-containing heterocyclic member selected from the group consisting of morpholino, piperazino, pyrrolidino, piperidino, hexamethyleneimino, pyrryl, indolyl, imidazolyl, benzimidazolyl, pyrazolyl, 1,3-oxazolidino, and 1,3-thiazolidino; esters of the type WHEREIN R7 is selected from the group consisting of alkyl having from one to eight carbons inclusive, trichloromethyl, and lower alkenyl having from two to four carbon atoms, inclusive, and the radical -(CH2)m-SR in which m is 1 or 2, R is alkyl having one to six carbon atoms, alkenyl having two to four carbon atoms, phenyl, substituted phenyl in which said substituents are selected from the group halogen, lower alkyl having one to four carbon atoms, inclusive, and lower alkoxy having one to four carbon atoms, inclusive; lower alkyl sulfonato having from one to six carbon atoms, inclusive; lower alkyl substituted thiophosphoryl wherein the lower alKyl groups independently contain from one to four carbon atoms, inclusive, and 2,2,2trichloro-1-hydroxyethyl, 4-cyanophenyl, 2,4,5-trichlorophenyl and 4-methylthiophenyl. The compounds are useful are insecticides, animal contact and systemic parasiticides, herbicides and foliar fungi protectants. Representative compounds are: 3-(0,0-diethylphosphorothioyl) benzaldoxime; 3-(O-(O,O-diethylphosphorothioyl)) -benzaldoximinoN&#39;&#39;-methyl carbamate; 4(O-O,O-diethylphosphorothioyl))acetophenone oxime; 4-(0,0-diethylphosphorothioyl))acetophenoneoximino-N&#39;&#39;-methyl carbamate; and 4-(0,0diethylphosphorothioyl)-acetophenoneoximino acetate; 4-(0-(0,0Diethylphosphorothioyl))-benzaldoximino-N&#39;&#39;-morpholinyl carbamate; 4-(O-(O,O-Diethylphosphorothioyl))-benzaldoximino-N&#39;&#39;-piperidyl carbamate; 4-(O,O-Diethylphosphorothioyl))-benzaldoximino-N&#39;&#39;azepinocarbamate; O-Ethyl-O-(4-(N&#39;&#39;-methylcarbamyl-oximino)phenyl) -N-methylamido phosphorothioate; 4-(O,O-Diethylphosphorothioyl))benzaldoximino-N&#39;&#39;-( Beta -N&#39;&#39;&#39;&#39;, N&#39;&#39;&#39;&#39;carbamate.

United States Patent Gutman [54] OXIME CARBAMATE PHOSPHATE,

PHOSPHONATE, PHOSPHINATE AND PHOSPHOROAMIDATES [72] Inventor: Arnold D. Gutman, Berkeley, Calif.

Stauffer Chemical Company, New York, NY.

[22] Filed: June 25, 1970 [21] Appl. No.: 49,936

Related US. Application Data [60] Division of Ser. No. 730,588, May 20, 1968, abandoned, which is a continuation-in-part of Ser. No. 646,467, June 16, 1967, abandoned.

[73] Assignee:

[51] Int. Cl. ..Co7f 9/32, Aoln 9/36 [58] Field of Search ..260/944, 926

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1,556,060 l/l969 France ..260/926 Primary Examiner.loseph Rebold Assistant ExaminerAnton H. Sutto Attorney-Daniel C. Block, Edwin H. Baker, Albert J. Adamcik and Harry A. Pacini [57] ABSTRACT Oxime carbamate phosphates, phosphonates, phosphinates and phosphoroamidates having the general formula:

Q R X in which X and Y are independently selected from the group consisting of oxygen and sulfur; R is selected from the group lower alkyl or lower alkoxy, having from one to six carbon atoms inclusive; R is selected from the group consisting of lower alkyl or lower alkoxy having from one to six carbon atoms, inclusive, amino, lower alkyl-substituted amino and phenyl; Q is selected from the group consisting of divalent tetramethylenediene-l,3, lower alkoxy or lower alkyl having from one to four carbon atoms inclusive, each, nitro, halogen and combinations thereof, and lower dialkyl-substituted thionophosphoryloxy; R is selected from the the group consisting of hydrogen, lower alkyl having from one to four carbon atoms, and phenyl; and R is selected from the group consisting of hydrogen; substituted carbonate and thiocarbonates of the type [151 3,681,476 [451 Aug. 1,1972

in which Z is oxygen or sulfur, R4 is lower alkyl having from one to four carbon atoms, inclusive, and B- chloro-loweralkyl having from two to four carbon atoms; carbamates of the type in which R and R are independently selected from the group consisting of hydrogen, alkyl having from one to ten carbons, inclusive, substituted alkyl having one to six carbon atoms inclusive, said substituents selected from the group consisting of hydroxy, halogen, amino, di-lower-alkyl amino, lower alkoxy, and tetrahydrofuryl; lower alkenyl having from two to four carbons, inclusive, carboalkoxy alkyl having a total of from three to eight carbon atoms, inclusive, cycloalkyl having from three to six carbon atoms, inclusive, piperazino, 2-thiazolyl, phenyl, naphthyl, substituted phenyl wherein said substituents are selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower thioalkyl, lower dialkylamino in which said lower alkyl and lower alkoxy moieties have from one to four carbon atoms, inclusive, nitro, cyano, trifluoromethyl, and combinations thereof; and in which is an N-containing heterocyclic member selected from the group consisting of morpholino, piperazino, pyrrolidino, piperidino, hexamethyleneimino, pyrryl, in dolyl, imidazolyl, benzimidazolyl, pyrazolyl, 1,3-oxazolidino, and l,3-thiazolidino; esters of the type wherein R is selected fromthe group consisting of alkyl having from one to eight carbons inclusive, trichloromethyl, and lower alkenyl having from two to four carbon atoms, inclusive, and the radical -(CH ,,,-SR in which m is l or 2, R is alkyl having one to six carbon atoms, alkenyl having two to four carbon atoms, phenyl, substituted phenyl in which said substituents are selected from the group halogen, lower alkyl having one to four carbon atoms, inclusive, and lower alkoxy having one to four carbon atoms, inclusive; lower alkyl sulfonato having from one to six carbon atoms, inclusive; lower alkyl substituted thiophosphoryl wherein the lower alkyl groups independently contain from one to four carbon atoms, inclusive, and 2,2,2-trichloro-l-hydroxyethyl, 4- cyanophenyl, 2,4,5-trichlorophenyl and 4- methylthiophenyl.

The compounds are useful are insecticides, animal contact and systemic parasiticides, herbicides and foliar fungi protectants. Representative compounds are: 3-[0,0-diethylphosphorothioyl] benzaldoxime; 3- [O-( 0,0-diethylphosphorothioyl -benzaldoximino-N' -methy l carbamate; 4[O-0,0-

United States Patent Gutman diethylphosphorothioyl)]acetophenone oxime; 4- [0,0-diethylphosphorothioyl)]-acetophenoneoximino- N-methyl carbamate; and 4-(0,0- diethylphosphorothioyl)-acetophenoneoximino acetate; 4-[0-(0,0-Diethylphosphorothioyb]-benzaldoximino-N'-morpholinyl Diethylphosphorothioyl) ]-benzaldoximin0-N piperidyl carbamate;

4-[0,0- Diethylphosphorothioyl) -benzaldoximino-N- carbamate; 4-[O-(0,0-

[151 3,681,476 1 Aug. 1,1972

azepinocarbamate; O-Ethyl-O-[4-(N'-methylcarbamyl-oximino)phenyl]-N-methylamido phosphorothioate; 4-[0,0-Diethylphosphorothioyl)]-benzaldoximino-N'- (,B-N, N"carbamate.

5 Claims, No Drawings This application is a division of copending application, Ser. No. 730,588, filed May 20, 1968, now abandoned which application is a continuation-in-part of then copending application, Ser. No. 646,467, tiled June 16, 1967, now abandoned.

This invention relates to certain novel phosphorus containing compounds which can be used as insecticides, animal parasiticides, both contact and systemic, herbicides and foliage fungi protectants. More specifically, this invention relates to certain substituted organo-oxime phosphates, phosphonates, phosphinates and phosphoroamidates and to the preparation and utility of the compounds as insecticides, animal systemic parasiticides, herbicides and foliage fungicides.

The compounds comprising the instant class of compounds correspond to the general formula:

QX Br in which X AND Y are independently selected from the group consisting of oxygen and sulfur; R is selected from the group lower alkyl or lower alkoxy, having from one to six carbon atoms, inclusive; R, is selected from the group consisting of lower alkyl or lower alkoxy having from one to six carbon atoms, inclusive, amino, lower alkyLsubstituted amino, and phenyl; Q is selected from the group consisting of divalent tetramethylenediene-l,3, lower alkoxy or lower alkyl having from one to four carbon atoms inclusive, each, nitro, halogen and combinations thereof, and lower dialkyl substituted thionophosphoryloxy; R is selected from the group consisting of hydrogen, lower alkyl having from one to four carbon atoms and phenyl; and R is selected from the group consisting of hydrogen substituted carbonate and thiocarbonates of the type in which 2 is oxygen or sulfur, R is lower alkyl having from one to four carbon atoms, inclusive, and B chloroloweralkyl having from two to four carbon atoms; carbamates of the type in which R and R are independently selected from the group consisting of hydrogen, alkyl having from one to 10 carbons, inclusive, substituted alkyl having one to six carbon atoms inclusive, said substituent is selected from the group consisting of hydroxy, halogen, amino, di-lower alkyl amino, lower alkoxy and tetrahydrofuryl; lower alkenyl having from two to four carbons, inclusive, carboalkoxy alkyl having a total of from three to eight carbon atoms, inclusive, cycloalkyl having from three to six carbon atoms, inclusive, piperazino, 2- thiazolyl, phenyl, naphthyl, substituted phenyl wherein said substituents are selected from the group consisting of halogen, lower alkyl, lower alkoxy, lower thioalkyl, lower dialkylamino in which said lower alkyl and lower alkoxy moieties have from one to four carbon atoms, inclusive, nitro, cyano, trifluoromethyl and combinations thereof; and in which is an N-containing heterocyclic member selected from the group consisting of morpholino, piperazino, pyrrolidino, piperidino, hexamethyleneimino, pyrryl, indolyl, imidazolyl, benzimidazolyl, pyrazolyl, 1,3-oxazolidino, and 1,3-thiazolidino; esters of the type wherein R is selected from the group consisting of alkyl having from one to eight carbons, inclusive, trichloromethyl, and lower alkenyl having from two to four carbon atoms, inclusive, and the radical (CI-I SR in which m is l or 2, R is alkyl having one to six carbon atoms, alkenyl having two to four carbon atoms, phenyl, substituted phenyl in which said substituents are selected from the group halogen, lower alkyl having one to four carbon atoms, inclusive and lower alkoxy having one to four carbon atoms, inclusive; lower alkyl sulfonato having from one to six carbon atoms, inclusive; lower alkyl substituted thiophosphoryl wherein the lower alkyl groups independently contain from one to four carbon atoms, inclusive; and 2,2,2-trichloro-l-hydroxyethyl, 4- cyanophenyl; 2,4,5-trichlorophenyl and 4- methylthiophenyl. Lower alkyl and lower alkoxy includes those members of the groups which contain the indicated number of carbon atoms in both straight chain and branched chain configurations. Lower alkenyl includes those members of the group containing a double bond and containing from two to four carbon atoms, inclusive. When Q is divalent tetramethylenel,3'it is bonded to the 2,3 or 3,4 carbon atoms of phenyl ring, thereby becoming either a or B naphthyl, respectively. Also included herein is a method of preparing, using, and applying the compositions.

The compounds herein described can be prepared by several methods. One such general method applicable in preparing the compounds is the condensation between the appropriate substituted phosphorus-containing oxy or thio benzaldehyde, e.g. phosphoro, phosphono, and phosphino, and hydroxylamine hydrochloride in order to prepare the corresponding benzaldoxime. The benzaldoxime can be further reacted with appropriate substituted isocyanate, substituted acid chlorides, substituted chloroformate, substituted chlorothiolformate, substituted sulfonyl chloride, monosubstituted carbamyl chloride, N,N-disubstituted carbamyl chloride, substituted phosphoryl chloride, substituted thionophosphoryl chloride, or anfollowed by the condensation with a primary or secondary amine. The reactions proceed readily in the liquid phase. The employment of a solvent is also useful, facilitating processing, as well as agitation of the reactants. Solvents such as water, benzene, toluene, chloroform, aqueous ethanol and the like, can be employed. When using derivatives containing the aldoxime, it is preferred to carry out the reaction in the presence of a hydrogen halide acceptor such as sodium carbonate, triethylamine, pyridine, picoline and the like, which are used as catalysts. Similarly, in the condensation reaction to prepare secondary carbamyl derivatives, the reaction is preferably conducted in the presence of a hydrogen halide acceptor.

The reactions are carried out at temperatures that permit operation in the liquid phase. These temperatures are between about room temperature and reflux temperature of the solvent, if one is employed. Preferably, the reaction mixture is refluxed, usually at an elevated temperature. The ketoxime can be reacted with functional moieties as described supra for the benzaldoxime.

It now has been discovered that the new compositions disclosed herein are distinguished as useful as insecticides, herbicides, foliar fungi protectants and are particularly effective as systemic parasiticidal agents for animals.

The compounds of the present invention are prepared in accordance with the following illustrative examples.

EXAMPLE 1 Preparation of the Intermediate diethylphosphorothioyl)lbenzaldehyde.

In 200 ml. of methyl ethyl ketone in a 500 ml. 3-neck flask are combined 24.4 g. (0.2 moles) 3-hydroxybenzaldehyde, 37.8 g. (0.2 moles) 0,0- diethylthiophosphorylchloride, and 16.4 g. (0.12 moles) potassium carbonate. The mixture is stirred and heated under reflux for 4 hours, cooled, and poured into 300 ml. of water. The mixture is filtered free of solid and is extracted with two 150 ml. portions of chloroform. The chloroform phases are combined, dried with anhydrous MgSO, and the solvent evaporated. There is obtained 54.7 g. (99.5 percent of theory) of the title intermediate, n 1.5239.

Preparation of 3-[0,0-diethylphosphorothioyl] benzaldoxime.

In 300 ml. of water are combined 27.4 g. (0.1 moles) 3-[O-(0,0-diethylphosphorothioyl)]-benzaldehyde and 7.6 g. (0.1 moles) hydroxylamine hydrochloride. The mixture is stirred at room temperature, and 7.5 g. (0.06 moles) sodium carbonate monohydrateis added over a period of min. The resulting mixture is stirred at room temperature for l hour. The mixture is extracted with two 150 ml. portions of benzene. The benzene phases are combined, dried with anhydrous MgSO, and evaporated. There is obtained a yield of 20.0 g. (68.3 percent of theory) of the title compound, n 1.5460.

EXAMPLE 2 Preparation of 3-[ 0-0,0-diethylphosphorothioyl benzaldoximino-N'-methyl carbarnate.

Ten grams (0.034 moles) of 3-[0-(0- diethylphosphorothioyl)] -benzaldoxime dissolved in 10 ml. of acetone is treated with an excess of methylisocyanate. The mixture is poured into 200 ml. of benzene. The benzene is washed with two 50 ml. portions of water, dried with anhydrous MgSO and evaporated. There is obtained a yield of 11.2 g. (93.3

percent of theory) of the title compound, n 1.5394.

EXAMPLE 3 Preparation of 4[O-(0,0- diethylphosphorothioyl)]- acetophenone oxime.

In 150 ml. of percent aqueous ethanol are combined 56.2 g. (0.195 moles) 4-[O(0,0- diethylphosphorothioyl)l-acetophenone, 17.4 g. (0.25 moles) hydroxylamine hydrochloride, and 4 gms. (0.1 mole) sodium hydroxide. The mixture is heated and reflux for 5 min., cooled, acidified with concentrated hydrochloride acid and extracted with two ml. portions of chloroform. The chloroform phases are combined, dried with anhydrous MgSO and evaporated. There is obtained 55.0 g. (93.5 percent of theory) of the title compound, n 1.5393.

EXAMPLE 4 Preparation of 4-[0-(0,0-diethylphosphorothioyl)1- acetophenoneoximino-N-methyl carbamate.

By an analogous procedure as given in Example 2, supra, 10.0 g. (0.03 moles) of 4-[O-(0,0- diethylphosphorothioyl ]-acetophenoneoxime is reacted with methyl isocyanate. There was obtained 1 1.5 g. (96.9 percent of theory) of the title compound.

EXAMPLE 5 Preparation of 4-[0,0-diethylphosphorothioyl]- acetophenoneoximino acetate.

The following procedure also can be used with a carbamy] chloride, sulfonyl chloride or chlorofomate in order to obtain compounds that include the respective functional moieties typical of said reactants.

In 150 ml. of benzene 10.0 g. (0.03 moles) of 4-[4- (0,0-diethylphosphorothioyl l-acetophenoneoxime, 3.2 g. (0.04 moles) of acetylchloride, and 4.1 g. (0.04 moles) of triethylamine are combined. The mixture is heated and refluxed for about l hour. The cooled reaction mixture is washed with two 50 ml. portions of water. The benzene phase is dried with anhydrous magnesium sulfate and then the benzene evaporated. There is obtained 11.0 g. (96.5 percent of theory) of the title compound n 1.5279.

EXAMPLE 6 Preparation of 4-[O-(0,0-diethylphosphorothioyl)] benzaldoximino-N'-morpholinylca.rbamate.

Seven grams (0.07 moles) of phosgene in 150 ml. of anhydrous diethyl ether is added to a 500 ml. threeneck flask fitted with a stirrer, dropping funnel, dry ice condenser, and thermometer. The solution is stirred and cooled to C. with an ice bath. N,N- dimethylaniline, 8.6 g. (0.07 moles) is added over a mixture is stirred at room temperature for 1 hour. The product is isolated by the procedure described in Example 6. There is obtained a 17.8 grams (94.8 percent period of 30 minutes. 4-[O-(0,0- of theory) of the title compound, n l .5423. diethylphosphorothioyl)]benza1doxime, 14.5 g. (0.05 5 moles) in 50 ml. of anhydrous diethyl ether is added EXAMPLE 8 over a period of 30 minutes. The temperature of the reaction mixture is maintained between 10 and C. preparation f 4 [O (O,o diethylphosphorothioyl)1 After the addition is complete, the mixture is stirred for benzaldoximinoNl ]B (N'1N1l diethylamino)ethylleap 1 hour at 15 C. A solution of 17.4 grams (0.2 moles) of 10 bamam morpholine and 10 ml. of water is added to the stirring Seven grams 0 07 moles) f phosgene, 5 grams reaction mixture at such a rate that the temperature (007 moles) f NNdimetMlaniline, and 145 grams does not exceed 15 After the add1t1on 1s complete, 5 moles) f 4 [O (O O di th ho h othi l)] the m1xture1sst1rredfor2 hours at room temperature. benzaldoxime are reacted in 1 f anhydrous The m1xture1s d luted w1th 200 ml. of ether and wash d di h l th r by the procedure described in Example 6. T- lf wlth 100 of water 100 1 N g The etherical solution is washed with 100 ml. of ice 8 1 wlth 100 of Water- The P cold 1N HCl and returned to the reaction flask where it due-d wlth anhydrous 8 4 and evaporated to yleld is stirred and cooled to 10 C. A solution of 1 1.6 grams grams pe of ry) of H 10.1 moles) of B-N,N-diethyl ethylenediamine and 10 dlethylpllosphorothloyl)]b3%nZaldX1mmN ml. of water is added to the etherical solution at such a morpholmylcarbamate rate that the temperature does not exceed 15 C. After the addition is complete, the mixture is stirred at room EXAMPLE 7 temperature for 1 hour. An additional 100 ml. of an- Preparation of -1 y p y )l hydrous diethyl ether is added, andthe mixture is beBZaIdOXimiIIO-N-(B y y y Cafbamatewashed with 50 ml. of ice cold 1N NaOl-I followed by Seven grams moles) of p g grams two 50 ml. portions of water. The ether phase is dried moles) of N,N-dimethy1ani1ine and grams with anhydrous MgSO 4 and evaporated. There is ob- (0.05 moles) of 4-[O-(0,0-diethylphosphorothioyl)] tained 1 1.3 grams (51.8 percent of theory) of the title benzaldoxime are reacted in 200 m1. anhydrous diethyl compound, n 1.5310. ether by the procedure described in Example 6. The The following is a table of the compounds prepared etherical solution is cooled to 10 C. and a solution of according to the aforedescribed procedures. Com- 6.1 grams (0.1 moles) of ethanolamine and 10 ml. of pound numbers have been assigned to each compound water is added at such a rate that the temperature does and are assigned used for identification throughout the not exceed 15 C. After the addition is complete, the balance of the application.

TABLE 1 Q R x i Y l R1 C=N0-Ra Compound M.P. C.) number R1 X Y Q (p) R5 o 0.1110 s 0 H- 3 H 1.5450 0,11 0 5 o 11. 4 11 1.5520 0.1110 s o H. 3 C(O)NHCH5-. 1. 5304 011110 s 0 11- 4 040151110111" 2 34-95 051110 s o 11. 4 C(O)NHCH1CH=OH1 1.5430 0.1110 s o 11 2 H 1. 5405 0.1110 s o H 4 c o o111 1.531s 011110 s 0 H- 2 010 N110111 1.5354 @1110 s 0 H 2 o o 1-r1ro1no1r=o111 1.5330 0.1110 s 0 11. 4 C(O)NH(OH5)3CH1.- 1. 5255 011110 s 0 11- 2 C(OH)HCC1; 1.5458 011.0 s 0 11. 4 11 1. 5055 011.0 s 0 11. 4 C(O)NIICH1 1.5533 C1110 S 0 II 3 1.5494 011.0 s 0 11 3 11 c omuoua 1.5400 (111.0 s 0 3 11 C(O)NIICII(CII1)1 1.5247 c1110 0 4 11 C(0 N11011 0111)1... 1.5421 (1,1110 s 0 4 11... 11 1.5410 11 0 S 0 4 II. C(O)NllOll; 1.5431: 0,1110 s o 4 11. o o m1c1no1 1.5303 011.0 s o 4 11 11 1.55115 c1110 5 0 4 1.5510 (1.1110 s o 3 1.5348 011.0 s o 4 1. 5570 c1110 5 0 1 4 1.5323 (1,11 0 h 0 3 1.5004 0 11 0 S 3 1.53411 (111 0 S. U 4 1.511112 1:11.40 5 1 4 1.5527 311110 3 0 4 1.5303 (111150 S 0 4 (1 11 0 S O 4 1.5382 (3.1110 s o 4 1.5253 011.0 s 0 3 1.5105 011.0 s o 3 1.5128 (2.1110 s o 4 1. 5153 CHaO S O 2 1.5665 011.10 s 0 2 1.5375 0.1150 s 0 2 1.5435 c1110 s 0 2 1.

M.P. C.) m

Table l Continued "n u u ICIIIII mIIII HHHHHHHHnwHHHHHHHHHHHHHH orHHHHHHHEH H HHH OOOOOOOOOOOOOOOOOOOOOOOO00000000000OOOOOOOOOOOOOOOOOOOOOOO SSSSSSSSSSSSSSSSSSSSSSSssssSSSSBSsssssssssssssssssssssssSSS Compound number =NOR;] relative to the phosphorus containing group.

Pre-emergence Herbicide Test The seeds of crab grass (CG) (digitaria sanguinalis (L.) Scop.), foxtail (Ft) (Setaria glauca (L.) Beauv.), 5 watergrass (WG) (Echinochloa crusgalli (L.) Beauv.), pigweed (PW) (Amaranthus retroflexus (L.), mustard (Md) (Brassica juncea (L.) Coss.), and curly dock (CD) (Rumex crispus (L.)), were planted in individual rows one-half inch deep in Santa Cruz sandy loam soil 55 contained in compressed paper flats 8 A X 6 inches, which are 2 inch deep. Enough seeds were planted to he give about to plants of each of the weed species is meant an amount of in each flat. The flats were watered after planting. The following day each flat was sprayed at the rate of 20 pounds of the candidate compound under test in 80 gallons of solution per acre. An atomizer was used to spray the solution on the soil surface. The flat were placed in a greenhouse at 80 F. and watered regularly. Two weeks laterthe degree of weed control was determined by comparing the amount of germination and growth of each weed in the treated flats with weeds in several untreated control flats. The results of this test are reported in Table II.

=Position of phenyl substitution by ecomposition.

HEREICIDAL SCREENING TESTS Dark oil.

Semi-solid.

Waxy solid.

Novel compositions are phytotoxic compounds which are useful and valuable in controlling various plant species.

In the method of the present invention for controlling undesirable plants which comprises applying an herbicidally effective amount of the above-described compounds to the area in which the control is desired, an herbicide is used to mean a compound which controls or modifies the growth of plants. By an bicidally effective amount compound which causes a modifying effect upon the growth of plants Such modifying effects include all deviations from natural development, for example, killing, retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, dwarfing and the like. By plants it is meant germinant seeds, emerging seedlings, and established vegetation including the roots and above-ground portions.

The compounds of this invention were tested as herbicides in the following manner.

Post-emergence Herbicide Test The seeds of four weed species, crab grass (CG) (digitaria sanguinalis (L) Scop.), watergrass (WG) (Echinochloa crusgalli (L.) Beauv.), red oats (R) (Avena sativa (L.)), mustard (Md) (Brassica juncea (L.) Coss.), and one crop, pinto beams (PB) (Phaseo- [us vulgaris) were planted in individual rows as described in the pre-emergence test, supra. Two weeks after planting, the plant foilage was sprayed with a 0.5 percent solution of the test compounds at a rate equivalent to 12.5 pounds/acre. The treated plants were placed back in the greenhouse. Injury ratings were recorded 14 days after treatment. The rating system is the same as that used in the pre-emergence test. Table [11 lists the results obtained therefrom.

TABLE II Pre-Emergence Herbicide Test* Compound Number l0 1 l *Herbicidal Activity Rating: slight injury -l+= moderate injury -H+= severe injury or death TABLE Ill Post-Emergence Herbicide Test* Compound Number i i i HHF 8 I ii I It I tiiiiiiis imiiiiii I HHiE In i++l||lllllllllllillllIllillllllllll Ml I42 ii ii iiiiiiiiiiii ii ii iii i i ii i li+l|l||||lilllliiilllll-FillIliIlIll|+|$l+||+l|+ itiiiiiiiii I iii I Hiiiiiiii I iitiiiiii iiiiiiiii I I i Hi I .I I +i I I I I I I iiiiiiiii I i I nit Hit i i 1 I M Herbicidal Activity Rating: -l= slight injury H moderate injury +H-= severe injury or death The compounds of the present invention are used as preemergence or post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice, the compounds areformulated with an inert carrier, utilizing methods well known to those skilled in the art, thereby making them suitable for application as dusts, sprays, or drenches and the like in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions, oil and water, water in oil emulsions, with or without the addition of wetting, dispersing or emulsifying agents. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application varies from i to approximately 50 pounds per acre.

The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-dusters, boom and hand sprayers and spray-dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. in order to modify or control growth of germinating seeds or emerging seedlings, the dust and liquid compositions are applied to the soil according to conventional methods and are preferably distributed in the soil to a depth of at least one-half inch below the soil surface. It is not necessary that the phytotoxic compositions be admixed with the soil particles and these compositions can be applied merely by spraying or sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions, granular compositions or liquid formulations applied on the surface of the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Phytotoxicants useful in combination with the abovedescribed compounds include for example 2,4- dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof; traizine derivatives, such as 2,4-bix( 3-methoxy-propylamino)-6- methylthio-S-triazine; 2-chloro-4-ethylamino-6- isopropylamino-S-triazine, and 2-ethylamino-4- isopropylamino-6-methylmercapto-S-triazine; urea derivatives, such as 3-(3,4-dichlorophenyl)-l ,1- dimethyl urea and 3-(p-chlorophenyl)-l ,l-dimethyl urea, and acetamides such as N,N-diallyl-achloroacetamide, N-(a-chloroacetyl)hexamethylene imine, and N,N-diethyl-a-bromoacetamide, and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic and; thiocarbamates, such as S-propyl dipropylthiocarbamate; S-ethyldipropylthiocarbamate, S-ethyl-cyclohexylethylthiocarbamate, S-ethyl hexahydro-lH-azepine-l-carbothioate and the like. Fertilizers useful in combination with the active ingredients include, for example, ammonium nitrate, urea and superphosphate. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

The compositions of the present invention were tested as foliage fungicides. This test indicated protectant action against fungi attacking plant foliage. Pinto bean plants were sprayed with three concentrations of dissolved or suspended chemical in water, 1,000, 500 and 100 parts per million (ppm). The active compound was dissolved in an appropriate solvent and further dispersed in water, and for this purpose a surface active agent or wetting agentwas employed to facilitate formulation of the dispersions. After the sprayed plants were dried, they were inoculated with powdery mildew spores (Erysiphe polygoni). Results were read when disease symptoms were distinct on untreated bean plants. Compound numbers 84 and 86 exhibited 75-99 percent control at 100 ppm. and compound number 85 exhibited 100 percent control at 100 ppm. of the powdery mildew infection with no phytotoxicity.

Insecticidal Evaluation Tests The following insect species were subjected to evaluation tests for insecticidal activity:

1. Housefly (HF) Musca domestica (Linn.)

2. German Roach (GR) Blattella germanica (Linn) 3. Salt-march caterpillar (SMC) Estigmene acrea 14 (Drury) 4. Milkweed Bug (MWB) Oncopeltus fagciatus (Dallas) 5. Lygus Bug (LB) Lygus hesperus (Knight) Aliquots of the toxicants, dissolved in an appropriate solvent, were diluted in water containing 0.002 percent of a wetting agent, Sponto 221 (a polyoxyether of alkylated phenols blended with organic sulfonates). Test concentrations ranged from 0.1 percent downward to that at which 50 percent mortality was obtained. In the tests, for these species, 10 l-month old nymphs of the German Cockroach and Lygus Bug and 2-week old nymphs of milkweed bug were placed in separate circular cardboard cages sealed on one end with cellophane and covered by a cloth netting on the other. Test concentrations for the Lygus Bug ranged from 0.05 percent downward to that at which 50 percent mortality was obtained. Each of the aqueous suspensions of the candidate compounds were sprayed onto the insects through the cloth netting by means of a hand spray gun. Percent mortality in each case recorded after 72 hours and the LD-SO values expressed as percent of toxicant in the aqueous spray was recorded.

For testing the Salt Marsh Caterpillar, test solutions were prepared in an identical manner and at concentrations the same as for the German cockroach and the milkweed bug above. Sections of bitter dock (Rumex obtusifolus) leaves, 1 1.5 inches in length were immersed in the test solutions for 10 to 15 seconds and placed on a wire screen to dry. The dried leaf was placed on a moistened piece of filter paper in a Petri dish and infested with five 3rd Instar larvae. Mortality of the larvae was recorded after 72 hours and the LD-SO values are expressed as percent active ingredient in the aqueous suspension.

The following procedure was used to test houseflies. A stock solution containing p. g/ml of the toxicant in an appropriate solvent was prepared. Aliquots of this solution werecombined with l milliliter of an acetonepeanut oil solution in a glass Petri dish and allowed to dry. The aliquots were there to achieve desired toxicant concentration ranging from 100p. g per Petri dish to that at which 50 percent mortality was attained. The Petri dishes were placed in a circular cardboard cage, closed on the bottom with cellophane and covered on top with cloth netting. Twenty-five female houseflies were introduced into the cage and the percent mortality was recorded after 48 hours. The LD-SO values are expressed in'terms of [L g per 25 female flies. The result of these insecticidal evaluation tests are given in Table IV.

33 10 0.1 0.05 0.1 36 20 0.1 0.1 37 3 0.1 0.005 0.1 38 3 0.1 0.003 0.1 39 8 0.1 0.05 0.05 40 8 0.1 0.03 0.1 41 3 0.1 0.05 0.08 42 0.1 0.05 0.05 46 8 0.1 0.05 0.03 47 8, 0.1 0.005 0.05 48 80 0.1 005 01 49 5 0.1 0.008 0.1 50 8 0.1 0.05 0.1 51 50 0.1 0.05 0.1 52 10 0.1 0.05 0.1 53 100 0.1 0.05 0.1 54 2.5 0.01 0.005 0.01 55 0.8 0.005 0.001 0.01 56 1.5 0.01 0.001 0.03 59 10 0.1 0.1 60 30 0.1 0.1 61 30 0.1 0.1 62 30 01 0.1 63 30 0.1 0.1 64 4 0.05 0.05 65 8 0.05 0.08 66 8 0.1 0.03 0.1 67 15 0.1 0.03 0.1 68 40 0.1 0.05 0.1 69 50 0.1 0.05 0.1 70 3O 0.1 0.05 0.1 71 7 0.1 0.03 0.05 78 8 0.1 0.03 0.05 84 5 0.1 0.005 0.1 85 8 01 0.01 0.05 89 7 0.1 0.05 01 94 8 0.1 0.05 0.1 101 2.5 0.05 0.005 0.01 104 6 0.03 0.008 0.05 105 7 0.03 0.01 0.005 106 7 0.03 0.01 0.008 107 3 0.03 0.005 0.003 108 7 0.03 0.01 0.005 109 3 0.03 0.008 0.1 110 6 0.03 0.01 0.1 l 1 1 7 0.1 0.03 0.03 112 7 01 0.05 0.1 118 4 0.1 0.005 0.008 121 8 0.1 0.01 0.03 122 5 0.1 0.01 0.1 124 5 0.05 0.005 0.01 126 5 0.1 0.008 0.1 130 5 0.03 0.003 0.01 133 5 0.1 0.05 0.1 137 6 0.1 0.005 0.03 138 5 0.1 0.03 0.01 142 6 0.03 0.003 0.05 143 4 0.03 0.01 0.03 149 5 0.03 0.03 0.03 152 l 4 0.08 0.008 0.05 155 4 0.1 0.03 0.1 157 3 0.05 0.008 0.01 6 0.03 0.01 0.001 171 3 0.03 0.005 0.03 172 3 0.01 0.005 0.005 8 0.1 0.01 0.1 186 9 0.1 0.03 0.1 187 5 0.1 0.01 0.1 191 4 0.1 0.005 0.05 192 2 0.03 0.003 0.03 195 7 0.1 005 0.1 200 8 0.1 0.03 0.05

In testing against milkweed bug representative LD-SO results obtained were for compound numbers 47, 55 and 56 0.01 percent; for compound numbers 49, 67 and 143 0.03 percent; compound number 64 1 6 0.05 percent; compound number 68 0.08 percent and compound number 54 0.008 percent. V

Compound number 5 5 is extremely useful in the control of European corn borer (Pyrausta nubilalis (Hubner)).

The same test procedure as mentioned above for salt marsh caterpillar was used for cotton bollworm (Heliothis zea (Boddie)), except that leaves of Romaine lettuce were utilized as the host plant rather 10 than bitter dock. The following compounds were found to be active against cotton bollworm: the LDS0 values obtained were (5), (54) and 143) 0.005 percent; (10) 0.01 percent; (13) 0.03 percent; (137) 0.001 percent; (55), (138), (141), and (142) 0.003 percent; and (56) 0.008 percent.

The compounds were also found to be active against two-spotted mite (Tetranychus urticae (Koch)). Lima bean plants (Phaseolus sp.) were utilized as the host plant and infected with 50 to 75 mites of various ages. Twenty-four hours after infestation, they were sprayed to the point of run off with aqueous suspension of the toxicant. Test concentrations range from 0.05 percent to that at which 50 percent mortality was obtained. The following compounds exhibited LD-SO values of 0.005

percent (9) and (56); 0.001 percent (55) and 0.008

percent (46).

The compounds were also found to be active against black bean aphid (Aphis fabae (Scop.)). The same test procedure as given for the two-spotted mite above was used for black bean aphid except that nasturtium (Tropaeolum sp.) plants approximately 2 to 3 inches tall were used as the host plant. The following compounds exhibited LD-50 values of 0.005 percent (40); 0.005 percent (55); 0.003 percent (37), 0.003 percent (38); 0.003 percent (65); 0.008 percent (56); and 0.008 percent (64).

Animal Systemic Evaluation Tests Candidate test compounds, usually formulated in Tween 20 (polyoxyethylene (20) Sorbitan monolaurate), are administered orally by stomach tube at an initial dosage of 400 mg/Kg. to fasted male Swiss albino mice. Two hours after treatment, the mice are killed by cervical dislocation and both thighs are dissected from each test animal and placed in labeled glass vials. Each vial is inoculated with 10 newly hatched black blow fly larvae (Phormia Regina (Meigen)) and stored in an incubator at 80 F. and 40-50 percent relative humidity. Tissues from mice that die during the 2 hour holding period after administration of the compounds are processed in the same manner. After the larvae had fed on the tissues for 48 hours, the vials are examined and the percentage of larvae mortality in each is noted. If 80 percent or more of the larvae are killed at the initial dosage, successively lower dosages are then tested until the lowest dosage that killed at least 80 percent of the larvae is determined.

In this animal systemic insecticide evaluation test, compounds are tested further on guinea pigs, using the oral route of administration. The compounds are formulated as solutions or suspensions in Tween 20 and administered at an initial dosage of 100 mgJKg. Twenty-four hours prior to treatment, the guinea pigs are wounded and the wounds infested with larvae of the black blow fly (Phormia Regina (Meigen)). At 4 and 24 hours after treatment, stable flies (Smmoxys calcitrans mouse assay and guinea pig assay tests described above.

TABLE V Animal Systemic Insecticide Activity Lowest Dosage (mg/Kg) Mouse Assay Guinea Pig Assay 90% Activity Against Stable Compound Lethal 80% Lethal Blow Fly Flies (4 Number to Mice Active to G; Pig Larvae hrs.)

(mg/Kg) (mg/Kg) (mg/Kg) (mg/Kg) 17 400 50 100 100 32 400 50 100 25 25 33 400 100 100 50 100 36 400 50 100 100 50 19 400 200 100 I 50 39 100 50 100 100 46 200 25 100 I00 100 48 400 200 100 100 51 400 200 100 100 60 400 200 100 100 100 61 400 200 100 100 65 100 50 100 50 50 66 200 50 50 25 25 67 200 100 50 50 25 84 200 100 200 100 50 86 400 200 100 100 100 87 400 50 50 O 25 94 200 100 100 100 50 133 100 200 134 400 25 135 400 50 136 400 100 137 100 50 138 100 25 139 400 100 141 50 144 400 100 145 400 100 146 400 100 148 400 100 149 50 25 150 400 200 151 I00 50 152 200 200 The test results indicate that these compounds are biologically active and are useful as animal systemic insecticides. The compounds can be used as effective parasiticides by applying them in a variety of ways and at various concentrations, depending upon the nature and habitat of the parasite to be controlled.

The candidate compounds were employed in an in vitro tick assay. In this test unfed lone star tick nymphs (Amblyomma americanum (L.)) were confined for 24 18 hours in cotton cloth thathad been treated in acetone solutions of the test compounds. The percentage of nymphal mortality was then observed. If 80 percent or more of the nymphs were killed at the initial screening level of 1.0 percent for a given compound, the compound was tested further at lower levels. The compounds 5, ll, 17, 20, 23, 26, 31, 33, 36, 38, 61, 64 and 65 exhibited 80 percent or better control of the tick nymphs at 0.5 percent. Compound number 29 exhibited 80 percent or better control of the tick nymphs at 0.1 percent and compound number 32 exhibited percent or better control at 1.0 percent concentrations. Compound number 28 at a concentration of 0.05 percent was better than 80 percent lethal to tick nymphs. lntemal animal parasite systemic tests The following procedures describe the chemoprophylactic and chemotherapeutic efficacy tests utilized to demonstrate the animal parasitology activity of the phosphorus-containing oxirne carbamate compositions of the present invention.

Test 1. Unparasitized weanling mice were offered medicated food for l 2 days prior to inducing infections, and for a total of 21 days infections were administered per os using 100 300 embryonated ova/mouse of Syphacia obvelata (So) and 100 300 embryonated ova/mouse of Aspiculun's tetraptera (At).

A suitable number of unmedicated littermate mice also received the above infection and served as control to determine the comparative efficacy of the medications. All mice were sacrificed after 21 days (the medication period) and the residual parasites found in the intestine were identified and counted. These counts in the medicated groups were compared to the unmedicated (controls) and a percent efficacy was assigned, (M/lCXl0O)-= percent efficacy.

Test 2. Weanling mice were housed together with older pinworrn (So) and (At) infected mice in a box with damp litter for 15 to 21 days to allow a heavy pin worm infection containing all stages of oxyurid (So and At) to naturally build up. At the end of this holding period, the post-weanling littermates were weighed individually and dosed with the subject compounds (suspended in Tween 20) on a body weight basis. One to 3 days later, these mice were sacrificed and the residual worms identified, counted and compared to the unmedicated controls. Examples of efficacy observed for six compounds of the present invention are given in the following table.

TABLE VI Internal Animal Systemic Activity Dosage: Efficacy Compound Test (1) ppm or Number Procedure (2) rug/Kg So At 2 (1) 500 100 100 2 (1) 2000 80 100 2 (2) 50 85 2 (2) 100 65 85 9 (1) 500 100 100 9 (1) 1000 100 100 17 (1) 1000 98 97 17 (1) 2000 55 17 (2) 50 30 0 17 (2) 45 30 17 (2) 200 55 100 46 (1) 250 100 100 46 (2) S0 85 75 46 (2) 100 100 100 66 (1) 1000 100 100 i9 29 66 (2) 65 100 compound employed, as described herein as well as 66 2 100 80 100 76 (2) 5o 92 upon whether the administration 15 to be a single dose 76 (2) 100 100 98 or a multiple dose over a period of daysln general, it gg 8g 82 has been found that the systemic parasiticides of this ini3 (3 202g g? 5 ventioglcar lzie admgnstered orally or parinterallly to warm e amrn s in amounts rangmg rom a out 29 (I) 1000 98 100 0.01 to about 600 milli rams per kilogram of bod i9 2 so 9s 65 gm g y s 1) 250 100 100 wei 48 2 so 9s 85 51 (U 250 90 65 What is claimed 1s. (2) 5o 95 5' l0 1. A compound having the formula 79 (l) 500 120 igo 79 2 50 s 2 86 2 so 90 9s 87 (2) 50 100 100 R x Q 88 (2 50 98 80 \iL 101 2 50 100 100 102 2 50 100 85 (5 4 250 l00 100 =NO-Rs 1o 1 500 100 100 28 1 500 100 100 70 (l) 250 95 87 1g; 23g {8g 9,? in which X and are independently selected from 135 1 1 500 100 29 the group consisting of oxygen and sulfur; 123 3 :88 R is selected from the group lower alkyl or lower alkox havin from one to six carbon atoms, inclu 140 1 500 100 y g 141 1 500 100 sive; 144 1 500 100 100 145 in 500 100 R lower alkoxy having from one to six carbon :2; 1 3 100 atoms, inclusive; 150 izi 25 100 0 Q s y g 151 100 100 R is selected from the group consisting of hydrogen, 152 (2) 100 and lower alkyl having from one to four carbon atoms;

R is selected from the group consisting of a. lower alkyl sulfonato having from one to six carbon atoms, inclusive;

b. lower alkyl substituted thiophosphoryl wherein the lower alkyl groups independently contain from one to four carbon atoms, inclusive; and

c 2,2,2-trichloro-l -hydroxyethyl,4-cyanophenyl, 2,4,5-trichlorophenyl and 4-methylthiophenyl.

2. A compound according to claim 1 in which R is C H O, R is C H O, X is S, Y is O, Q is H, and the The compounds of the present invention are useful as effective insecticides, herbicides, and external and internal animal parasiticides and are applicable in a variety of ways at various concentrations. In practice, the compounds are formulated with an inert adjuvant utilizing methods well known to those skilled in the art, thereby making them suitable for application and administration as dusts, sprays, drenches and the like in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions, C(32) group is m the riuclear 4'posmon m oil-in-water, water-in-oil emulsions, with or without the which R2 15 H and W P F- addition of wetting, dispersing or emulsifying agents. A compound accorfhng to clam! 1 which R Administration of said parasiticidal compositions to CZHSO R1 15 (321150 Y Q fl h animal for systemic control of parasites can be in (32) N R? g p 1n the nuclear 'P animal feedstuffs which contain feed components of WhlchRe 1S a andRals )2 2 s)2- such as grain, grasses and the like, and certain benefi- 4. A compound according t0 claim 1 in WhiCh R is cial additives such as vitamins, proteins, fats,'minerals C 50, 1 iS C2H5O, X is S, Y is O, Q iS a d the and carbohydrates. They can be given also in drinking C(R NOR group is in the nuclear 4-position in water or skimmed milk, or in the form of tablets or capwhich R is CH, and R is P(S)(OC H sules. Further methods of application include sprays, 5. A compound according to claim 1 in which R is dyes, dips, dermal p subcutaneous admiuis- C,H,0, R, is C l-I 0, x is s, Y is 0 and Q is H, and the tration, intramuscular injection and the like. The exact C(RZ) NOR: group is in the nuclear LPosition i dose to be administered to the animal is dependent whichR2isHandR8iSc(01-])H CC13,

upon the parasite to be controlled by the particular 

2. A compound according to claim 1 in which R is C2H5O, R1 is C2H5O, X is S, Y is O, Q is H, and the C(R2)= NOR3 group is in the nuclear 4-position in which R2 is H and R3 is 4-methylthiophenyl.
 3. A compound according to claim 1 in which R is C2H5O, R1 is C2H5O, X is S, Y is O, Q is H, and the C(R2)= NOR3 group is in the nuclear 4-position in which R2 is CH3 and R3 is S(O)2CH2CH(CH3)2.
 4. A compound according to claim 1 in which R is C2H5O, R1 is C2H5O, X is S, Y is O, Q is H, and the C(R2)= NOR3 group is in the nuclear 4-position in which R2 is CH3 and R3 is P(S)(OC2H5)2.
 5. A compound according to claim 1 in which R IS C2H5O, R1 is C2H5O, X is S, Y is O and Q is H, and the C(R2)= NOR3 group is in the nuclear 2-position in which R2 is H and R3 is C(OH)H-CCl3. 